CN109844008B - Rubber composition and crosslinked rubber - Google Patents

Rubber composition and crosslinked rubber Download PDF

Info

Publication number
CN109844008B
CN109844008B CN201780064239.7A CN201780064239A CN109844008B CN 109844008 B CN109844008 B CN 109844008B CN 201780064239 A CN201780064239 A CN 201780064239A CN 109844008 B CN109844008 B CN 109844008B
Authority
CN
China
Prior art keywords
rubber
opening polymer
ring
polymer
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780064239.7A
Other languages
Chinese (zh)
Other versions
CN109844008A (en
Inventor
角替靖男
奥野晋吾
似鸟广幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Publication of CN109844008A publication Critical patent/CN109844008A/en
Application granted granted Critical
Publication of CN109844008B publication Critical patent/CN109844008B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/135—Cross-linked structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3322—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclooctene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention provides a rubber composition comprising a liquid monoene ring-opening polymer (B) in an amount of 1 to 100 parts by weight per 100 parts by weight of a solid rubber (A), wherein the weight average molecular weight (Mw) of the solid rubber (A) is 100000 or more, and the weight average molecular weight (Mw) of the liquid monoene ring-opening polymer (B) is 1000 to 50000.

Description

Rubber composition and crosslinked rubber
Technical Field
The present invention relates to a rubber composition containing a solid rubber and a liquid monoene ring-opening polymer, and more particularly to a rubber composition capable of forming a rubber crosslinked product having high tensile strength and excellent heat resistance and ozone resistance.
Background
Liquid diene elastomers such as liquid polybutadiene and liquid polyisoprene have double bonds in the polymer main chain and are excellent in rubber elasticity, and therefore, they are widely used as modifiers for improving rubber processability, hardness, mechanical strength and elongation by mixing with solid rubbers. In addition, in order to improve affinity for solid rubber, further improve affinity for inorganic fillers, and introduce crosslinking points, a modified liquid diene elastomer in which a modifying group is introduced into a liquid diene elastomer is known.
However, when such a liquid diene elastomer is blended with a solid rubber to prepare a rubber crosslinked product, there are problems that the mechanical strength such as tensile strength is insufficient and the heat resistance and ozone resistance are deteriorated. Therefore, a liquid elastomer having higher mechanical strength and excellent heat resistance and ozone resistance is required.
On the other hand, a technique for obtaining a cyclic olefin ring-opening polymer by subjecting a cyclic olefin to a metathesis ring-opening polymerization reaction in the presence of a chain transfer agent is known, and for example, patent document 1 discloses the following technique: in the presence of an olefin containing a modifying group, a cyclic olefin is subjected to metathesis ring-opening polymerization using a ruthenium catalyst to obtain a cyclic olefin ring-opening polymer having a modifying group at a terminal of a polymer chain. Patent document 1 discloses that the amount of a modifying group introduced into the obtained cyclic olefin ring-opening polymer can be adjusted by adjusting the ratio of the modifying group-containing olefin to the cyclic olefin.
Patent document 2 discloses a hydrogenated cyclic olefin ring-opening polymer in which a part of carbon-carbon double bonds in the main chain structure of a cyclic olefin ring-opening polymer having a weight average molecular weight of 1000 to 100000 is hydrogenated.
However, the techniques described in patent documents 1 and 2 do not disclose a technique for obtaining a liquid cyclic olefin ring-opening polymer as a cyclic olefin ring-opening polymer, and therefore cannot be applied as a substitute material for the liquid diene elastomer. In particular, in the technique of patent document 2, a cyclic olefin ring-opening polymer is hydrogenated to become a resin polymer by a hydrogenation reaction.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 11-514043;
patent document 2: japanese patent laid-open publication No. 2002-317034.
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, an object of the present invention is to: provided is a rubber composition which can be formed into a rubber composition having high tensile strength and excellent heat resistance and ozone resistance.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that the above object can be achieved by blending a liquid monocyclic olefin ring-opening polymer having a weight average molecular weight within a specific range with a specific amount to a solid rubber, and have completed the present invention.
That is, according to the present invention, there is provided a rubber composition containing a liquid monoene ring-opening polymer (B) in a proportion of 1 to 100 parts by weight relative to 100 parts by weight of a solid rubber (a), wherein the weight average molecular weight (Mw) of the solid rubber (a) is 100000 or more, and the weight average molecular weight (Mw) of the liquid monoene ring-opening polymer (B) is 1000 to 50000.
In the rubber composition of the present invention, it is preferable that the above-mentioned monocyclic olefin ring-opening polymer (B) is a polymer containing only a structural unit derived from a monocyclic monoene, or a copolymer containing a structural unit derived from a monocyclic monoene and a structural unit derived from a monomer copolymerizable with the monocyclic monoene.
In the rubber composition of the present invention, the monocyclic olefin ring-opening polymer (B) is preferably a polymer containing only a structural unit derived from cyclopentene, or a copolymer containing a structural unit derived from cyclopentene and a structural unit derived from a monomer copolymerizable with cyclopentene.
In the rubber composition of the present invention, it is preferable that the melt viscosity of the monocyclic olefin ring-opening polymer (B) is 3000 pas or less as measured at 25 ℃ with a Brookfield viscometer.
In the rubber composition of the present invention, the glass transition temperature of the monocyclic olefin ring-opening polymer (B) is preferably-50 ℃ or lower.
In the rubber composition of the present invention, it is preferable that the rubber (a) is at least 1 rubber selected from the group consisting of natural rubber, polyisoprene rubber, styrene butadiene rubber and polybutadiene rubber.
The rubber composition of the present invention preferably further contains an inorganic filler.
The rubber composition of the present invention preferably further contains a crosslinking agent.
Further, the present invention can provide a crosslinked rubber product obtained by crosslinking the rubber composition.
Effects of the invention
According to the present invention, there can be provided: a rubber composition capable of forming a rubber crosslinked product having high tensile strength and excellent heat resistance and ozone resistance, and a rubber crosslinked product having high tensile strength and excellent heat resistance and ozone resistance obtained by using the rubber composition.
Detailed Description
The rubber composition of the present invention contains a liquid monoene ring-opening polymer (B) in a proportion of 1 to 100 parts by weight relative to 100 parts by weight of a solid rubber (A), wherein the weight-average molecular weight (Mw) of the solid rubber (A) is 100000 or more, and the weight-average molecular weight (Mw) of the liquid monoene ring-opening polymer (B) is 1000 to 50000.
According to the present invention, by blending the liquid monoene ring-opening polymer (B) with the solid rubber (a), it is possible to increase the heat resistance and ozone resistance while maintaining high tensile strength when a rubber crosslinked material is produced.
< solid rubber (A) >
The solid rubber (a) used in the present invention is not particularly limited as long as it is a rubbery polymer having a weight average molecular weight (Mw) of 100000 or more and a solid state at room temperature (25 ℃) (exhibiting no fluidity at room temperature (25 ℃) and having shape retention properties). The Mooney viscosity (ML1+4, 100 ℃) of the solid rubber (A) measured in accordance with JIS K6300 is usually 20 or more.
The solid rubber (a) is not particularly limited, and examples thereof include Natural Rubber (NR), polyisoprene rubber (IR), Styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, emulsion-polymerized styrene-acrylonitrile-butadiene copolymer rubber, conjugated diene rubbers such as conjugated diene rubbers, ethylene propylene diene rubber (EPDM), ethylene-propylene rubber and other olefin rubbers; non-olefin rubbers such as acrylate rubbers, epichlorohydrin rubbers, fluororubbers, silicone rubbers, chloroprene rubbers, and urethane rubbers; and the like. Among them, olefin-based rubbers are preferable, conjugated diene-based rubbers are more preferable, and natural rubbers, polyisoprene rubbers, styrene butadiene rubbers, and polybutadiene rubbers are particularly preferable, because of high compatibility with the liquid monoene ring-opening polymer (B) and a large effect of increasing heat resistance and ozone resistance, which are effects of blending the liquid monoene ring-opening polymer (B).
The solid rubber (a) may be a solid rubber having a weight average molecular weight (Mw) of 100000 or more in terms of polystyrene as measured by gel permeation chromatography, and from the viewpoint of further improving the mechanical strength of the resulting rubber crosslinked product, a solid rubber having a weight average molecular weight (Mw) of 200000 or more is more preferable, and a solid rubber having a weight average molecular weight (Mw) of 300000 or more is even more preferable. The upper limit of the weight average molecular weight (Mw) is not particularly limited, but is preferably 2000000 or less.
< liquid monocyclic olefin Ring-opening Polymer (B) >
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention is a liquid polymer containing a repeating unit obtained by ring-opening polymerization of a monocyclic olefin as a repeating unit constituting a main chain thereof, and having a weight average molecular weight (Mw) of 1000 to 50000.
The proportion of the repeating unit obtained by ring-opening polymerization of a monocycloolefin in the liquid monocycloolefin ring-opening polymer (B) used in the present invention is preferably 70 mol% or more, more preferably 75 mol% or more, and still more preferably 80 mol% or more based on the total repeating units. However, the monocyclic olefin ring-opening polymer may contain a repeating unit derived from another monomer copolymerizable with the monocyclic olefin, as long as the properties of the monocyclic olefin ring-opening polymer are maintained, and the proportion of the repeating unit derived from the other monomer is preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less, based on the total repeating units. The monocyclic olefin is a hydrocarbon compound having a carbon-carbon double bond in a ring formed by one ring, and the number of the carbon-carbon double bonds may be 1 or more (however, it does not contain an aromatic ring).
Specific examples of such monocyclic olefins include monocyclic monoenes having 1 carbon-carbon double bond in the ring, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene; monocyclic dienes having 2 carbon-carbon double bonds in the ring, such as 1, 4-cyclohexadiene, 1, 4-cycloheptadiene, 1, 5-cyclooctadiene; monocyclic trienes having 3 carbon-carbon double bonds in the ring, such as 1,5, 9-cyclododecatriene, and the like. Among them, monocyclic monoene is preferable, and cyclopentene is more preferable from the viewpoint of compatibility with the solid rubber (a). The monocyclic olefin may or may not have a substituent, and the substituent is not particularly limited, and examples thereof include an alkyl group such as a methyl group and an ethyl group.
Examples of the other monomer copolymerizable with the monocyclic olefin include polycyclic cyclic olefins, polycyclic cyclic dienes, and polycyclic cyclic trienes. Examples of the polycyclic cyclic monoene, polycyclic cyclic diene and polycyclic cyclic triene include 2-norbornene, dicyclopentadiene, 1, 4-methylene-1, 4,4a,9 a-tetrahydro-9H-fluorene and tetracyclo [6.2.1.13,6.02,7]Norbornene compounds which may have substituents such as dodec-4-ene. Among them, polycyclic cyclic monoene and polycyclic cyclic diene are preferable, and 2-norbornene and dicyclopentadiene are more preferable.
When the liquid monocyclic olefin ring-opening polymer (B) is a copolymer, it may be any of the following copolymers: a copolymer of 1 kind of monocyclic olefin and 1 or 2 or more kinds of monomers other than monocyclic olefin, or a copolymer of 2 or more kinds of monocyclic olefin, and further a copolymer of 2 or more kinds of monocyclic olefin and 1 or 2 or more kinds of monomers other than monocyclic olefin. When the monocyclic olefin ring-opening polymer has 2 or more structural units derived from a monocyclic olefin, the proportion of all the structural units derived from a monocyclic olefin contained in the monocyclic olefin ring-opening polymer may be in the above range.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention is preferably a polymer comprising a repeating unit constituting its main chain, a structural unit derived from only a monocyclic monoene, or a copolymer comprising a structural unit derived from a monocyclic monoene and a structural unit derived from a monomer copolymerizable with the monocyclic monoene (also comprising a structural unit derived from a monocyclic olefin other than the monocyclic monoene), and more preferably a polymer comprising a structural unit derived from only cyclopentene, or a copolymer comprising a structural unit derived from cyclopentene and a structural unit derived from a monomer copolymerizable with cyclopentene (also comprising a structural unit derived from a monocyclic olefin other than cyclopentene), from the viewpoint of compatibility with the solid rubber (a), from the viewpoint of excellent heat resistance and ozone resistance. As the monomer copolymerizable with cyclopentene, monocyclic dienes, polycyclic cyclic monoenes, polycyclic cyclic dienes are preferable, and 1, 5-cyclooctadiene, 2-norbornene, and dicyclopentadiene are more preferable.
When the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is a polymer containing a structural unit derived from a monocyclic monoene, the proportion of the structural unit derived from a monocyclic monoene is preferably 70 mol% or more, more preferably 75 mol% or more, and still more preferably 80 mol% or more, based on the total repeating units. On the other hand, the proportion of the structural unit derived from a monomer copolymerizable with a monocyclic monoene is preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less, based on the total repeating units.
When the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is a polymer containing a structural unit derived from cyclopentene, the proportion of the structural unit derived from cyclopentene is preferably 70 mol% or more, more preferably 75 mol% or more, and still more preferably 80 mol% or more based on the total repeating units. On the other hand, the proportion of the structural unit derived from a monomer copolymerizable with cyclopentene is preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less, relative to the total repeating units.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention has a weight average molecular weight (Mw) of 1000 to 50000, preferably 1500 to 45000, and more preferably 2000 to 40000, as a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography. When the weight average molecular weight (Mw) is too low, the mechanical strength such as tensile strength of the resulting rubber crosslinked product is deteriorated, while when the weight average molecular weight (Mw) is too high, the monocyclic olefin ring-opening polymer does not take on a liquid state.
The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the liquid monocyclic olefin ring-opening polymer (B) used in the present invention in terms of polystyrene as measured by gel permeation chromatography is not particularly limited, and is usually 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less. By setting the Mw/Mn ratio within the above range, the mechanical strength such as tensile strength of the resulting rubber crosslinked product can be further improved.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention is a liquid polymer, that is, a polymer having a liquid state at room temperature (25 ℃) (having fluidity at room temperature (25 ℃)), specifically, a polymer having fluidity at room temperature (25 ℃) at which the melt viscosity measured at 25 ℃ using a brookfield viscometer is about 3000Pa · s or less. In the present invention, by using such a liquid monoene ring-opening polymer (B), the solid rubber (a) can be blended well, and thus the resulting rubber crosslinked product can have high tensile strength and excellent heat resistance and ozone resistance. The melt viscosity at 25 ℃ of the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is preferably 2000Pa · s or less, more preferably 1000Pa · s or less, and further preferably 300Pa · s or less.
The cis/trans ratio of the double bonds present in the repeating units constituting the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is not particularly limited, and is preferably in the range of 15/85 to 60/40, and more preferably in the range of 15/85 to 40/60, from the viewpoint of further improving heat resistance and ozone resistance. Having cis/trans ratio enabling the ring-opening of the polymer (B) by a monocyclic olefin in liquid form13C-NMR spectrum measurement.
The method of adjusting the cis/trans ratio of the liquid monocyclic olefin ring-opening polymer (B) to the above-mentioned range is not particularly limited, and examples thereof include a method of controlling polymerization conditions in the case of polymerizing a monocyclic olefin to obtain a liquid monocyclic olefin ring-opening polymer (B). For example, the higher the polymerization temperature at the time of polymerizing the monocyclic olefin, the higher the trans ratio can be made, and the lower the monomer concentration in the polymerization solution, the higher the trans ratio can be made.
The glass transition temperature (Tg) of the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is preferably-50 ℃ or lower, more preferably-60 ℃ or lower, and still more preferably-70 ℃ or lower, from the viewpoint of providing the resulting rubber crosslinked product with excellent low-temperature characteristics and rubber elasticity. The glass transition temperature of the liquid monocyclic olefin ring-opening polymer (B) can be adjusted, for example, by: the cis/trans ratio of the double bond present in the repeating unit is adjusted, for example, when the liquid monocyclic olefin ring-opening polymer (B) is a copolymer, the content ratio of the structural unit derived from a monomer copolymerizable with the monocyclic olefin is adjusted.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention may have a melting point (Tm) within the above range as measured at a temperature of 25 ℃ using a brookfield viscometer, and when the liquid monocyclic olefin ring-opening polymer (B) has a melting point, the melting point (Tm) is preferably less than 25 ℃. When the melting point (Tm) of the liquid monocyclic olefin ring-opening polymer is less than 25 ℃, the effect of the present invention can be easily obtained when the monocyclic olefin ring-opening polymer is a liquid polymer at room temperature (25 ℃). The melting point (Tm) of the liquid monocyclic olefin ring-opening polymer (B) can be adjusted, for example, by: the cis/trans ratio of the double bonds present in the repeating units is adjusted, and the type and content ratio of the repeating units contained in the liquid monocyclic olefin ring-opening polymer (B) are adjusted. For example, the melting point (Tm) can be lowered by increasing the content ratio of the cyclopentene unit and the 1, 5-cyclooctadiene unit in the monocyclic olefin monomer units constituting the liquid monocyclic olefin ring-opening polymer (B). On the other hand, when the content ratio of the cyclooctene unit is increased, the melting point (Tm) may be increased, and the rubber properties at room temperature may be deteriorated.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention may have a molecular structure formed of only carbon atoms and hydrogen atoms, or may have a molecular structure containing atoms other than carbon atoms and hydrogen atoms, and more specifically may have a modifying group containing an atom selected from the group consisting of an atom belonging to group 15 of the periodic table, an atom belonging to group 16 of the periodic table, a silicon atom and a halogen atom in a side chain or at a polymer chain end.
From the viewpoint of affinity with the inorganic filler when the inorganic filler is blended, the modifying group is more preferably a modifying group containing an atom selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a silicon atom and a halogen atom, and among them, a modifying group containing an atom selected from a nitrogen atom, an oxygen atom and a silicon atom is further preferred. Specific examples of such a modifying group include an amino group, a hydroxyl group, a hydroxycarbonyl group, a carboxylic anhydride group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an oxysilyl group, a halogen atom and the like, and among them, an amino group, a hydroxyl group, a hydroxycarbonyl group, a methacryloyloxy group, an oxysilyl group are preferable. Specific examples of the oxysilyl group include an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group, an alkylsiloxysilyl group, an arylsilyloxysilyl group, and a hydroxysilyl group, and among them, an alkoxysilyl group is preferable. The alkoxysilyl group is a group in which 1 or more alkoxy groups are bonded to a silicon atom, and specific examples thereof include trimethoxysilyl group, (dimethoxy) (methyl) silyl group, (methoxy) (dimethyl) silyl group, triethoxysilyl group, (diethoxy) (methyl) silyl group, (ethoxy) (dimethyl) silyl group, (dimethoxy) (ethoxy) silyl group, (methoxy) (diethoxy) silyl group, tripropoxysilyl group, and tributoxysilyl group.
The liquid monocyclic olefin ring-opening polymer (B) used in the present invention may have a modifying group introduced only at one polymer chain end (single end), may have a modifying group introduced at both polymer chain ends (both ends), or may have both of them mixed. Further, a liquid monocyclic olefin ring-opening polymer into which a modifying group has been introduced and a liquid monocyclic olefin ring-opening polymer into which no modifying group has been introduced may be mixed.
The introduction ratio of the modifying group at the polymer chain end of the liquid monoene ring-opening polymer (B) is not particularly limited from the viewpoint of affinity with the inorganic filler when the inorganic filler is blended, and is preferably 60% or more, more preferably 80% or more, and further preferably 100% or more in terms of a percentage of the number of modifying groups relative to the number of polymer chains of the liquid monoene ring-opening polymer (B). The method for measuring the ratio of the modifying group introduced into the polymer chain end is not particularly limited, and can be determined by using1The peak area ratio corresponding to the modifier determined by H-NMR spectroscopy and the number average molecular weight (Mn) determined by gel permeation chromatography were determined.
The method for synthesizing the liquid monocyclic olefin ring-opening polymer (B) used in the present invention is not particularly limited as long as the target polymer can be obtained, and it can be synthesized by a conventional method, and examples thereof include a method of ring-opening polymerizing a monocyclic olefin-containing monomer in the presence of a molecular weight modifier by using a ruthenium carbene complex as a ring-opening polymerization catalyst.
The ruthenium carbene complex is not particularly limited as long as it is a ruthenium carbene complex which is a ring-opening polymerization catalyst for a monocyclic olefin. Specific examples of the ruthenium carbene complex which can be preferably used include: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3, 3-diphenylpropylidene ruthenium dichloride, dichloro- (3-phenyl-1H-inden-1-ylidene) bis (tricyclohexylphosphine) ruthenium (II), (3-phenyl-1H-inden-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) tert-butylvinylidene ruthenium dichloride, bis (1, 3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (3-dicyclohexylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1, 3-dicyclohexylimidazoline-2-ylidene) benzylidene ruthenium dichloride, (1, 3-dimethylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, ruthenium dichloride, (1, 3-xylylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride, (1, 3-xylylimidazolidin-2-ylidene) (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride, and the like.
The amount of the ruthenium carbene complex to be used is not particularly limited, and is usually in the range of 1: 2000 to 1: 2000000, preferably in the range of 1: 5000 to 1: 1500000, and more preferably in the range of 1: 10000 to 1: 1000000 in terms of a molar ratio (ruthenium metal in the catalyst: a monocyclic olefin-containing monomer). When the amount of the ruthenium carbene complex used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, when too much, there is a risk that: it becomes difficult to remove the catalyst residue from the obtained monocyclic olefin ring-opening polymer, and various properties are deteriorated when the polymer is formed into a rubber crosslinked product.
Examples of the molecular weight modifier include olefin compounds such as 1-butene, 1-pentene, 1-hexene, and 1-octene; diene compounds such as 1, 4-pentadiene, 1, 4-hexadiene, 1, 5-hexadiene, 1, 6-heptadiene, 2-methyl-1, 4-pentadiene and 2, 5-dimethyl-1, 5-hexadiene.
The amount of the molecular weight modifier used is not particularly limited, and may be set according to the intended weight average molecular weight (Mw), and is preferably 0.1 to 20 parts by weight, more preferably 0.15 to 15 parts by weight, and still more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the monocyclic olefin-containing monomer used for polymerization.
The polymerization reaction may be carried out in the absence of a solvent or in a solution. When the polymerization is carried out in a solution, the solvent to be used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the monocyclic olefin-containing monomer used for the polymerization, the polymerization catalyst, and the like, and a hydrocarbon-based solvent, an ether-based solvent, or a halogen-based solvent is preferably used. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane; alicyclic hydrocarbons such as cyclohexane, cyclopentane, methylcyclohexane, and the like. Examples of the ether solvent include diethyl ether, cyclopentylmethyl ether, 1, 2-dimethoxyethylene, and tetrahydrofuran. Examples of the halogen-based solvent include alkyl halogens such as methylene chloride and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene.
The polymerization temperature is not particularly limited, and may be usually set in the range of-50 to 100 ℃. The polymerization reaction time is preferably 1 minute to 72 hours, and more preferably 5 minutes to 20 hours. After the polymerization conversion rate reaches a predetermined value, a known polymerization terminator may be added to the polymerization system to stop the polymerization reaction.
When the liquid monocyclic olefin ring-opening polymer (B) has a modifying group at a polymer chain end, the ring-opening polymerization is preferably carried out in the presence of an olefin compound having a modifying group. Further, since the olefin compound having a modifying group acts as a molecular weight modifier in addition to the function of introducing the modifying group into the polymer chain end, it is desirable that the above-mentioned molecular weight modifier is not used when the olefin compound having a modifying group is used.
The olefin compound having a modifying group is not particularly limited as long as it contains at least 1 each of an ethylenically unsaturated bond and a modifying group in a molecule. Examples of the modifying group include an amino group, a hydroxyl group, a hydroxycarbonyl group, a carboxylic anhydride group, a methacryloyloxy group, an epoxy group, an oxysilyl group, and a halogen atom.
Examples of the olefin compound having an amino group include allylamine, N-allylaniline, N-allylbenzylamine, 4-aminostyrene, 2-butene-1, 4-diamine, and 3-hexene-2, 5-diamine.
Examples of the olefin compound having a hydroxyl group include allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 4-hexen-1-ol, 4-hepten-1-ol, 5-decen-1-ol, 5-hexen-1-ol, 5-octen-1-ol, 6-hepten-1-ol, 4-hydroxystyrene, 2-allylphenol, allyl 4-hydroxybenzoate, 1-cyclohexyl-2-buten-1-ol, ethylene glycol monoallyl ether, 3-allyloxy-1, 2-propanediol, 2-buten-1, 4-diol, 3-hexen-2, 5-diol, and the like.
Examples of the olefin compound having a hydroxycarbonyl group include 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, trans-3-pentenoic acid, vinylbenzoic acid, trans-3-hexenedioic acid and the like.
Examples of the olefin compound having a carboxylic anhydride group include allyl succinic anhydride and (2, 7-octadien-1-yl) succinic anhydride.
Examples of the olefin compound having a methacryloxy group include cis-1, 4-dimethacryloxy-2-butene, allyl methacrylate, and 5-hexenyl methacrylate.
Examples of the olefin compound having an epoxy group include 1, 3-butadiene monoepoxide, allyl glycidyl ether, 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene, and 1,2,9, 10-diepoxy-5-decene.
Examples of the olefin compound having an oxysilyl group include: alkoxysilane compounds such as vinyl (trimethoxy) silane, vinyl (triethoxy) silane, allyl (trimethoxy) silane, allyl (methoxy) (dimethyl) silane, allyl (triethoxy) silane, allyl (ethoxy) (dimethyl) silane, styryl (trimethoxy) silane, styryl (triethoxy) silane, 2-styrylethyl (triethoxy) silane, allyl (triethoxysilylmethyl) ether, and allyl (triethoxysilylmethyl) (ethyl) amine; aryloxy silane compounds such as vinyl (triphenoxy) silane, allyl (triphenoxy) silane, and allyl (phenoxy) (dimethyl) silane; acyloxy silane compounds such as vinyl (triacetoxy) silane, allyl (diacetoxy) methylsilane, and allyl (acetoxy) (dimethyl) silane; alkylsilyloxy silane compounds such as allyltris (trimethylsiloxy) silane; aryl siloxy silane compounds such as allyltris (triphenylsiloxy) silane; polysiloxane compounds such as 1-allylheptamethyltrisiloxane, 1-allylnonylmethyltetrasiloxane, 1-allylnonylmethylcyclopentasiloxane, and 1-allylundecylcyclohexasiloxane; alkoxysilane compounds such as 1, 4-bis (trimethoxysilyl) -2-butene, 1, 4-bis (triethoxysilyl) -2-butene, and 1, 4-bis (trimethoxysilylmethoxy) -2-butene; aryloxy silane compounds such as 1, 4-bis (triphenoxysilyl) -2-butene; acyloxysilane compounds such as 1, 4-bis (triacetoxysilyl) -2-butene; alkylsilyloxy silane compounds such as 1, 4-bis [ tris (trimethylsiloxy) silyl ] -2-butene; aromatic silyloxysilane compounds such as 1, 4-bis [ tris (triphenylsilyloxy) silyl ] -2-butene; polysiloxane compounds such as 1, 4-bis (heptamethyltrimethoxysilyloxy) -2-butene and 1, 4-bis (decamethylcyclohexylsiloxy) -2-butene.
Examples of the olefin compound having a halogen atom include allyl chloride, crotyl chloride, 1, 4-dichloro-2-butene, allyl bromide, allyl iodide, crotyl chloride, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene and the like.
These olefin compounds having a modifying group may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The amount of the olefin compound having a modifying group is not particularly limited, and may be set according to the introduction ratio of the modifying group into the polymer chain end of the liquid monoene ring-opening polymer (B) and the target weight average molecular weight (Mw), and is preferably 0.1 to 20 parts by weight, more preferably 0.15 to 15 parts by weight, and still more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the monomer containing a monoene used for polymerization. Further, since the olefin compound having a modifying group functions as a molecular weight regulator in addition to the function of introducing the modifying group into the polymer chain end of the liquid monocyclic olefin ring-opening polymer (B), it is also preferable to set the amount of the olefin compound having a modifying group to the above range from the viewpoint of controlling the weight average molecular weight (Mw) of the liquid monocyclic olefin ring-opening polymer (B) to the above range.
In the above manner, a polymer solution containing the liquid monocyclic olefin ring-opening polymer (B) can be obtained. The polymer solution can be recovered by a known recovery method. For example, the liquid monocyclic olefin ring-opening polymer (B) can be obtained by mixing a polymer solution with an excessive amount of a poor solvent for the polymer to precipitate the polymer, recovering the precipitated polymer, and drying it. Alternatively, the polymer solution may be directly dried, and unreacted monocyclic olefin and the solvent may be evaporated off to obtain a liquid monocyclic olefin ring-opening polymer (B).
Alternatively, the following method may be used: in synthesizing the liquid monocyclic olefin ring-opening polymer (B), instead of the above-described method using the ruthenium carbene complex as the ring-opening polymerization catalyst, a monomer containing a monocyclic olefin is ring-opening polymerized in the presence of a molecular weight modifier using a molybdenum compound or a tungsten compound as the ring-opening polymerization catalyst.
Specific examples of the molybdenum compound that can be used as a ring-opening polymerization catalyst include molybdenum pentachloride, molybdenum tetrachloride oxide, and molybdenum (phenylimide) tetrachloride. Specific examples of the tungsten compound include tungsten hexachloride, tungsten tetrachloride oxide, tungsten (phenylimide) tetrachloride, tungsten monophthalate tetrachloride, bis (3, 5-di-t-butyl) catechol tungsten dichloride, bis (2-chloroacetic acid) tetrachloride, and tungsten tetraphenyloxide oxide.
The same molecular weight modifier as used in the method using the ruthenium carbene complex can be used as the molecular weight modifier in the same amount.
When a molybdenum compound or a tungsten compound is used as the ring-opening polymerization catalyst, an organometallic compound may be used in combination as a catalyst promoter. As the organometallic compound which can be used as the catalyst auxiliary, there can be mentioned organometallic compounds having a metal atom of group 1,2, 12, 13 or 14 of the periodic Table having a hydrocarbon group of 1 to 20 carbon atoms. Among them, an organolithium compound, an organomagnesium compound, an organozinc compound, an organoaluminum compound, and an organotin compound are preferably used, an organolithium compound, an organotin compound, and an organoaluminum compound are more preferably used, and an organoaluminum compound is particularly preferably used. The amount of the organic metal compound used is not particularly limited, but is preferably 1: 0.1 to 10, more preferably 1: 0.5 to 5 in terms of a molar ratio of (molybdenum compound, tungsten compound: organic metal compound).
The polymerization reaction conditions and the like in the case where a molybdenum compound or a tungsten compound is used as the ring-opening polymerization catalyst can be appropriately set within the range of the conditions in the above-described method using a ruthenium carbene complex.
In the method of using a molybdenum compound or a tungsten compound as a ring-opening polymerization catalyst, when the liquid monocyclic olefin ring-opening polymer (B) has a modifying group at a terminal of a polymer chain, it is preferable to perform ring-opening polymerization in the presence of an olefin compound having a modifying group, as in the case of using a ruthenium carbene complex. However, since molybdenum compounds and tungsten compounds generally have low resistance to olefin compounds having a modifying group, it is preferable to use an olefin compound having a modifying group protected with a protecting group instead of an olefin compound having a modifying group.
For example, when the olefin compound having a modifying group is an olefin compound having an amino group, a hydroxyl group, or a hydroxycarbonyl group, a product protected with a protecting group such as an alkyl group, an acyl group, an RC (O) -group (provided that R is a saturated hydrocarbon group having 1 to 10 carbon atoms), a silyl group, or a metal alkoxide can be used. Alternatively, a product obtained by reacting an olefin compound having an amino group, a hydroxyl group, and a hydroxycarbonyl group with a trialkylaluminum compound may also be used. In addition, the amount of the olefin compound having a modifying group protected by a protecting group in this case may be the same as that in the case of using the ruthenium carbene complex described above.
In addition, when an olefin compound having a modifying group protected by a protecting group is used, deprotection is performed after the polymerization reaction. The method of deprotection is not particularly limited, and may be performed by a known method depending on the protecting group used. Specifically, methods such as deprotection by heating, deprotection by hydrolysis or alcoholysis, and the like can be given.
In the above manner, a polymer solution containing the liquid monocyclic olefin ring-opening polymer (B) can be obtained. As the method for recovering the polymer from the polymer solution, a known recovery method described in the above-mentioned case of using the ruthenium carbene complex can be employed.
In addition, an antioxidant such as a phenol stabilizer, a phosphorus stabilizer, or a sulfur stabilizer may be added to the liquid monocyclic olefin ring-opening polymer (B) obtained in the above manner as desired. The amount of the antioxidant to be added may be appropriately determined depending on the kind thereof. Further, an operation oil (Extender oil) may be added as desired.
< rubber composition >
The rubber composition of the present invention contains a liquid monocyclic olefin ring-opening polymer (B) in a proportion of 1 to 100 parts by weight relative to 100 parts by weight of the solid rubber (a).
The content of the liquid monocyclic olefin ring-opening polymer (B) in the rubber composition of the present invention is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, and more preferably 5 to 60 parts by weight, based on 100 parts by weight of the solid rubber (a). When the content of the liquid monoene ring-opening polymer (B) is too small, the effect of blending the liquid monoene ring-opening polymer (B), that is, the effect of increasing the heat resistance and ozone resistance in the case of producing a rubber crosslinked material, cannot be obtained. On the other hand, when the content of the liquid monocyclic olefin ring-opening polymer (B) is too large, the tensile strength of the resulting rubber crosslinked product is lowered.
The rubber composition of the present invention preferably contains an inorganic filler in addition to the solid rubber (a) and the liquid monoene ring-opening polymer (B). By incorporating an inorganic filler, the mechanical properties of the resulting rubber crosslinked material can be improved. Examples of the inorganic filler include metal powders such as aluminum powder; inorganic powders such as carbon black, hard clay, talc, calcium carbonate, titanium oxide, calcium sulfate, calcium carbonate, and aluminum hydroxide; organic powders such as starch and polystyrene powder; short fibers such as glass fibers (milled fibers), carbon fibers, aramid fibers, and potassium titanate whiskers; silica, mica, and the like. Among them, carbon black and silica are preferably used, and carbon black is particularly preferably used.
Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Among them, furnace black is preferably used, and specific examples thereof include SAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF-HS, HAF-LS, MAF, FEF and the like. They can be used individually or in combination of 2 or more.
Examples of silica include dry process silica, wet process silica, colloidal silica, and precipitated silica. Among them, wet process white carbon containing hydrous silicic acid as a main component is preferable. They can be used individually or in combination of 2 or more.
The amount of the inorganic filler in the rubber composition of the present invention is preferably 20 to 200 parts by weight, more preferably 25 to 150 parts by weight, and particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of the solid rubber (a). By setting the blending amount of the inorganic filler within the above range, the mechanical properties of the obtained rubber crosslinked material can be suitably improved.
The rubber composition of the present invention preferably further contains a crosslinking agent. The crosslinking agent is appropriately selected depending on the kind of the solid rubber (a), and examples thereof include sulfur, halogenated sulfur, organic peroxides, quinone dioxides, organic polyvalent amine compounds, zinc acrylates, and alkylphenol resins having a methylol group. Among them, sulfur is preferably used. The amount of the crosslinking agent to be incorporated in the rubber composition of the present invention is preferably 0.5 to 5 parts by weight, more preferably 0.7 to 4 parts by weight, and particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the solid rubber (a).
In addition, the rubber composition of the present invention may contain compounding agents such as a crosslinking accelerator, a crosslinking activator, an antiaging agent, an activator, a processing oil, a plasticizer, and a wax in a required amount by a conventional method.
Examples of the crosslinking accelerator include sulfenamide-based crosslinking accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide, N-tert-butyl-2-benzothiazylsulfenamide, N-oxyethylene-2-benzothiazylsulfenamide, and N, N' -diisopropyl-2-benzothiazylsulfenamide; guanidine crosslinking accelerators such as 1, 3-diphenylguanidine, 1, 3-ditolylbuanidine and 1-n-heptylbiguanide; a thiourea-based crosslinking accelerator; a thiazole-based crosslinking accelerator; a thiuram-based crosslinking accelerator; a dithiocarbamate-based crosslinking accelerator; and xanthic acid crosslinking accelerators. Among them, a crosslinking accelerator containing a sulfenamide-based crosslinking accelerator is particularly preferable. These crosslinking accelerators may be used individually or in combination of 2 or more. The amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid rubber (a).
Examples of the crosslinking activator include higher fatty acids such as stearic acid, and zinc oxide. The amount of the crosslinking activator is not particularly limited, and when a higher fatty acid is used as the crosslinking activator, the amount is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid rubber (a), and when zinc oxide is used as the crosslinking activator, the amount is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid rubber (a).
Mineral oil or synthetic oil can be used as the processing oil. As the mineral oil, aromatic oil, naphthenic oil, paraffinic oil, etc. can be usually used.
The method for obtaining the rubber composition of the present invention is not particularly limited, and the respective components may be kneaded according to a conventional method, and examples thereof include the following methods: the intended composition is obtained by kneading a compounding agent such as an inorganic filler, a solid rubber (a), and a liquid monocyclic olefin ring-opening polymer (B) in addition to the crosslinking agent and the thermally unstable component, and then mixing the kneaded product with the crosslinking agent and the thermally unstable component. The kneading temperature of the compounding agent such as an inorganic filler, the solid rubber (A) and the liquid monoene ring-opening polymer (B) is preferably 70 to 200 ℃ and more preferably 100 to 180 ℃ in addition to the crosslinking agent and the thermally unstable component. The kneading time is preferably 30 seconds to 30 minutes. The mixing of the kneaded product with the thermally unstable component is usually carried out after cooling to 100 ℃ or lower, preferably 80 ℃ or lower.
< crosslinked rubber >
The rubber crosslinked material of the present invention can be obtained by crosslinking the rubber composition of the present invention.
The crosslinking method is not particularly limited, and may be selected according to the shape, size, and the like of the crosslinked rubber. The rubber composition may be filled in a mold and heated to crosslink at the same time as molding, or a previously molded rubber composition may be heated to crosslink. The crosslinking temperature is preferably 120 to 200 ℃, more preferably 140 to 180 ℃, and the crosslinking time is usually about 1 to 120 minutes.
Further, depending on the shape and size of the rubber crosslinked material, the inside may not be sufficiently crosslinked although the surface is crosslinked, and therefore, the rubber may be further heated to be secondarily crosslinked.
As the heating method, general methods usable for rubber crosslinking, such as press heating, steam heating, oven heating, and hot air heating, can be appropriately selected.
The rubber crosslinked material of the present invention obtained in this manner is obtained by using the rubber composition of the present invention in which the liquid monoene ring-opening polymer (B) is blended in a proportion of 1 to 100 parts by weight relative to 100 parts by weight of the solid rubber (a), and therefore has high tensile strength and excellent heat resistance and ozone resistance. The crosslinked rubber of the present invention can be suitably used for various applications such as: various rubber members such as vibration-proof rubbers for vehicles such as railways and automobiles, gaskets for radiators, sealing materials for brake fluids, sealing materials for aqueous liquids, and various sealing materials for accumulator airbags; various rubber members such as vibration-proof rubbers, conveyor belts, electric wires, cables, and electrical insulating covering materials, and air springs used for various industrial machines; rubber materials for supporting bridges and buildings; sealing materials used in various fields such as aerospace field, ship field, etc., such as sealing materials, packages, rubber stoppers, and O-rings; fenders used in the marine field; adhesives, strength-imparting agents for adhesives, and the like.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" are based on weight unless otherwise specified. Further, various tests and evaluations were carried out according to the following methods.
[ weight average molecular weight (Mw) and number average molecular weight (Mn) of liquid monocyclic olefin Ring-opening Polymer ]
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the monocyclic olefin ring-opening polymer in a liquid state was carried out by a Gel Permeation Chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation) using two H-type columns HZ-M (manufactured by Tosoh Corporation) in series and tetrahydrofuran as a solvent at a column temperature of 40 ℃. The detector used was a differential refractometer RI-8320 (manufactured by Tosoh Corporation). The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the liquid monocyclic olefin ring-opening polymer were measured as values in terms of polystyrene.
[ glass transition temperature (Tg) and melting Point (Tm) of liquid monocyclic olefin Ring-opened Polymer ]
The temperature was measured at-150 ℃ to 40 ℃ at a temperature rise of 10 ℃ per minute using a differential scanning calorimeter (DSC, product name "X-DSC 7000", manufactured by Hitachi High-Tech Science Company).
[ composition ratio of monomer units in liquid monocyclic olefin Ring-opening Polymer ]
According to1The composition ratio of the monomer units in the liquid monocyclic olefin ring-opened polymer was determined by H-NMR spectroscopy.
[ melt viscosity of liquid monocyclic olefin Ring-opened Polymer ]
The melt viscosity at 25 ℃ was measured by a Brookfield viscometer DV-II + Pro (manufactured by Brookfield, Inc.). The shear rate in the measurement is 1.2 to 10sec in accordance with the viscosity-1And (4) adjusting.
[ introduction ratio of modifying group at end of polymer chain of liquid monocyclic olefin Ring-opening Polymer ]
Dissolving a liquid monocyclic olefin ring-opening polymer in deuterated chloroform, and subjecting a tritiated chloroform solution in which the liquid monocyclic olefin ring-opening polymer is dissolved to1H-NMR spectrum measurement to measure the ratio of the peak area integral value specific to the modifying group and the peak area integral value derived from the olefinAnd (4) determining. Then, based on the ratio of the integrated values of the peak areas measured and the measurement result of the number average molecular weight (Mn) by GPC, the introduction rate of the modifying group into the polymer chain end was calculated. The ratio of the number of modifying groups introduced into the polymer chain end to the number of liquid monocyclic olefin ring-opened polymer chains is defined as the ratio of the number of modifying groups to the number of liquid monocyclic olefin ring-opened polymer chains. That is, the modifying group introduction rate of 100% indicates a state in which the modifying group is introduced at a ratio of 1 to 1 molecule of the liquid monoene ring-opening polymer chain, and the modifying group introduction rate of 200% indicates a state in which the modifying group is introduced at both ends of the 1 molecule of the liquid monoene ring-opening polymer chain.
[ tensile Strength of crosslinked rubber ]
The sheet-like crosslinked rubber was punched in a dumbbell-shaped No. 6 shape in a direction parallel to the grain direction to obtain a dumbbell-shaped test piece. Then, the dumbbell test piece obtained was subjected to a tensile test according to JIS K6251 under conditions of 23 ℃ and 500 mm/min using a tensile tester (product name "TENOMETER 10K", manufactured by ALPHA TECHNOLOGIES, Inc.) as a tester, and the tensile strength S was measured0。
[ Change in tensile Strength before and after Heat treatment of crosslinked rubber ]
The dumbbell test pieces were obtained by the same tensile test as described above, and were heat-treated at 100 ℃ for 72 hours using a gear aging tester (product name "AG-1110", manufactured by Ueshima Seisakusho Co., Ltd.) to obtain heat-treated test pieces. Then, the heat-treated test piece was subjected to a tensile test in the same manner as the tensile test described above, and the tensile strength S of the heat-treated test piece was measured1. Then, from the obtained measurement results, the rate of change Δ S of the tensile strength before and after the heat treatment was obtained according to the following equation. It is preferable that the absolute value of the rate of change Δ S of the tensile strength before and after the heat treatment is smaller because the fluctuation due to the heat treatment is smaller.
The rate of change Δ S (%) of tensile strength before and after heat treatment { (tensile strength S after heat treatment)1(MPa) -tensile Strength S before Heat treatment0(MPa))/tensile Strength S before Heat treatment0(MPa)}×100
[ static ozone deterioration test ]
The dumbbell test piece was obtained by punching a sheet-like crosslinked rubber material in a dumbbell No. 1 shape. The dumbbell Test piece was subjected to a static Ozone deterioration Test using an Ozone aging Test chamber (Ozone weather meter) (product name "OMS. HN", Suga Test Instruments co., ltd. system) in accordance with JIS K6259 at a Test temperature of 40 ℃, an Ozone concentration of 50pphm, a tensile strain of 20%, and a Test time of 24 hours. The ozone resistance of the test piece after the ozone deterioration test was evaluated by observing the size of a crack in the test piece according to JIS K6259 by a crack state observation method.
The size of the test piece cracks was evaluated according to the following criteria.
1: cracks were not visible with the naked eye, and were confirmed with a magnifying glass of 10 times.
2: cracks can be visually confirmed.
3: the cracks were deep and large (less than 1 mm).
4: the cracks were deep and large (1mm or more and less than 3 mm).
5: cracks of 3mm or more or fractures are likely to occur.
[ Synthesis example 1]
Synthesis of liquid monocyclic olefin Ring-opened Polymer (B-1)
1000 parts of cyclopentene, 21.5 parts of 1-hexene, and 990 parts of toluene were charged into a pressure-resistant glass reaction vessel equipped with a magnetic stirrer under a nitrogen atmosphere. Next, 0.068 part of (3-phenyl-1H-inden-1-ylidene) bis (tricyclohexylphosphine) ruthenium (II) dissolved in 10 parts of toluene was added thereto, and polymerization was conducted at room temperature for 3 hours. After 3 hours of polymerization, the polymerization was terminated by adding an excess of vinyl ethyl ether, and then a large amount of methanol was added to precipitate the polymer. Then, after recovering the precipitate by removing the supernatant, the recovered precipitate was subjected to vacuum drying at 50 ℃ for 24 hours by removing the residual solvent with an evaporator to obtain 700 parts of a liquid monocyclic olefin ring-opening polymer (B-1). The obtained liquid monocyclic olefin ring-opening polymer (B-1) had Mw of 7600, Mn of 4600, Tg of-92 ℃ and Tm of 23 ℃. The melt viscosity measured at 25 ℃ was 9 pas.
[ Synthesis example 2]
Synthesis of liquid monocyclic olefin Ring-opening Polymer (B-2)
850 parts of a liquid monocyclic olefin ring-opening polymer (B-2) was obtained in the same manner as in synthesis example 1, except that 1000 parts of cyclooctadiene was used instead of 1000 parts of cyclopentene. The obtained liquid monocyclic olefin ring-opening polymer (B-2) had Mw 14800, Mn 8500, Tg-104 ℃, and no Tm was observed. The melt viscosity measured at 25 ℃ was 20 pas.
[ Synthesis example 3]
Synthesis of liquid monocyclic olefin Ring-opening Polymer (B-3) having hydroxyl group at both terminals
In a pressure-resistant glass reaction vessel equipped with a magnetic stirrer, 750 parts of cyclopentene, 250 parts of 2-norbornene, 28.2 parts of cis-2-butene-1, 4-diol, and 990 parts of tetrahydrofuran were charged under a nitrogen atmosphere. Next, 0.068 part of (3-phenyl-1H-inden-1-ylidene) bis (tricyclohexylphosphine) ruthenium (II) dissolved in 10 parts of tetrahydrofuran was added thereto, and polymerization was conducted at room temperature for 3 hours. After 3 hours of polymerization, the polymerization was terminated by adding an excess of vinyl ethyl ether, and then a large amount of methanol was added to precipitate the polymer. Then, after recovering the precipitate by removing the supernatant, the recovered precipitate was subjected to vacuum drying at 50 ℃ for 24 hours by removing the residual solvent with an evaporator to obtain 750 parts of a liquid monocyclic olefin ring-opening polymer (B-3) having a hydroxyl group at both ends. In the obtained liquid monocyclic olefin ring-opening polymer having a hydroxyl group at both ends (B-3), Mw 13400 and Mn 6300 were observed, and the content ratio of a monomer unit derived from cyclopentene, the content ratio of a monomer unit derived from 2-norbornene, the introduction ratio of a terminal-modifying group, Tg-72 ℃ were 88 mol%, and Tm was not observed. The melt viscosity measured at 25 ℃ was 15 pas.
[ example 1]
In a Banbury mixer, 100 parts of polybutadiene rubber (trade name "Nipol BR 1220", manufactured by Nippon Corporation, weight average molecular weight (Mw): 468000, Mooney viscosity (ML1+4, 100 ℃): 44, solid at room temperature) was masticated for 30 seconds, and then 50 parts of the liquid monoene ring-opening polymer (B-1) obtained in Synthesis example 1,2 parts of stearic acid, 3 parts of zinc oxide, 60 parts of CARBON black (trade name "IRB # 8", CONTINENTAL CARBON Co., manufactured by Ltd.), and 15 parts of a processing Oil (trade name "Aromax T-DAE", manufactured by JXTG Nippon Oil & Energy Corporation) were added thereto, and after kneading at 110 ℃ for 180 seconds, the compounding agent remaining on the plunger was cleaned, and then further kneaded for 150 seconds, and the kneaded mixture was discharged from the mixer. Next, the obtained kneaded mixture was cooled to room temperature, and then, the cooled kneaded mixture was kneaded with 1.5 parts of sulfur and 0.9 part of N- (tert-butyl) -2-benzothiazylsulfenamide (trade name "noceler NS-P", OUCHI SHINKO CHEMICAL industry co., ltd., product) as a crosslinking accelerator by using an open roll mixer at 23 ℃, thereby obtaining a rubber composition in a sheet form. Next, the obtained rubber composition was press-crosslinked at 160 ℃ for 20 minutes to obtain a sheet-like crosslinked rubber product having a thickness of 1 mm. Then, using the sheet-like crosslinked rubber obtained, the tensile strength and the rate of change in the tensile strength before and after the heat treatment, and the static ozone deterioration test were performed in the same manner as described above. The results are shown in Table 1.
[ example 2]
A rubber composition and a rubber crosslinked material were obtained in the same manner as in example 1 except that 20 parts of the liquid monoene ring-opening polymer (B-2) obtained in synthesis example 2 was used in place of 50 parts of the liquid monoene ring-opening polymer (B-1), and evaluations were performed in the same manner as in example 1. The results are shown in Table 1.
[ example 3]
A rubber composition and a rubber crosslinked material were obtained in the same manner as in example 1 except that 10 parts of the liquid monocyclic olefin ring-opening polymer (B-3) having a hydroxyl group at both ends, which was obtained in synthesis example 3, was used instead of 50 parts of the liquid monocyclic olefin ring-opening polymer (B-1), and evaluations were performed in the same manner as in example 1. The results are shown in Table 1.
[ example 4]
A rubber composition and a rubber crosslinked material were obtained in the same manner as in example 1 except that 100 parts of natural rubber ("SMR-CV 60" weight average molecular weight (Mw): 633000 and Mooney viscosity (ML1+4, 100 ℃ C.): 60, solid at ordinary temperature) was used in place of 100 parts of polybutadiene rubber, and evaluations were made in the same manner as in example 1. The results are shown in Table 1.
[ example 5]
A rubber composition and a rubber crosslinked material were obtained in the same manner as in example 1 except that 100 parts of styrene butadiene rubber (trade name "Nipol NS 616", manufactured by Nippon Raynaud Co., Ltd., weight average molecular weight (Mw): 426000) and Mooney viscosity (ML1+4, 100 ℃ C.): 62) were used instead of 100 parts of polybutadiene rubber, and evaluations were made in the same manner as in example 1. The results are shown in Table 1.
Comparative example 1
A rubber composition and a crosslinked rubber were obtained in the same manner as in example 1 except that 20 parts of liquid polybutadiene (trade name: Krasol LBH-P3000 ", manufactured by Cray Valley, Inc., having a weight-average molecular weight (Mw): 3400 and a melt viscosity of 20 pas measured at 25 ℃) was used instead of 50 parts of liquid monocyclic olefin ring-opening polymer (B-1), and evaluations were made in the same manner as in example 1. The results are shown in Table 1.
Comparative example 2
A rubber composition and a rubber crosslinked material were obtained in the same manner as in example 1 except that 50 parts of the liquid monocyclic olefin ring-opening polymer (B-1) was not blended, and evaluation was performed in the same manner as in example 1. The results are shown in Table 1.
[ Table 1]
Figure GDA0003082930930000211
As shown in table 1, the rubber crosslinked material obtained using the rubber composition in which the liquid monoene ring-opening polymer (B) is blended in a proportion of 1 to 100 parts by weight relative to 100 parts by weight of the solid rubber (a) has high tensile strength, is suppressed in the rate of change Δ S in tensile strength before and after heat treatment, and is excellent in heat resistance and further excellent in ozone resistance.
On the other hand, when liquid polybutadiene was used as the liquid polymer, the absolute value of the change rate Δ S of the tensile strength before and after the heat treatment was large, the heat resistance was poor, and further the ozone resistance was poor (comparative example 1).
In addition, in the case where no liquid polymer was blended, the absolute value of the change rate Δ S of the tensile strength before and after the heat treatment was large, the heat resistance was poor, and further the ozone resistance was poor (comparative example 2).

Claims (9)

1. A rubber composition comprising 1 to 60 parts by weight of a liquid monocyclic olefin ring-opening polymer B per 100 parts by weight of a solid rubber A,
the weight average molecular weight Mw of the solid rubber A is 100000 or more, the weight average molecular weight Mw of the liquid monocyclic olefin ring-opening polymer B is 1000 to 50000,
the solid rubber a is at least one selected from the group consisting of Natural Rubber (NR), polyisoprene rubber (IR), Styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, emulsion-polymerized styrene-acrylonitrile-butadiene copolymer rubber, ethylene propylene diene rubber (EPDM), ethylene-propylene rubber, acrylate rubber, epichlorohydrin rubber, fluororubber, silicone rubber, chloroprene rubber, and urethane rubber.
2. The rubber composition according to claim 1, wherein the monocyclic olefin ring-opening polymer B is a polymer containing only a structural unit from a monocyclic monoene or a copolymer containing a structural unit from a monocyclic monoene and a structural unit from a monomer copolymerizable with the monocyclic monoene.
3. The rubber composition according to claim 1 or 2, wherein the monocyclic olefin ring-opening polymer B is a polymer containing only a structural unit derived from cyclopentene, or a copolymer containing a structural unit derived from cyclopentene and a structural unit derived from a monomer copolymerizable with cyclopentene.
4. The rubber composition according to claim 1 or 2, wherein the melt viscosity of the monocyclic olefin ring-opening polymer B is 3000Pa s or less as measured at a temperature of 25 ℃ using a Brookfield viscometer.
5. The rubber composition according to claim 1 or 2, wherein the glass transition temperature of the monocyclic olefin ring-opening polymer B is-50 ℃ or lower.
6. The rubber composition according to claim 1 or 2, wherein the rubber A is at least 1 rubber selected from natural rubber, polyisoprene rubber, styrene butadiene rubber and polybutadiene rubber.
7. The rubber composition according to claim 1 or 2, further containing an inorganic filler.
8. The rubber composition according to claim 1 or 2, further containing a crosslinking agent.
9. A crosslinked rubber product obtained by crosslinking the rubber composition according to claim 8.
CN201780064239.7A 2016-10-31 2017-10-25 Rubber composition and crosslinked rubber Active CN109844008B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016-212962 2016-10-31
JP2016212962 2016-10-31
PCT/JP2017/038509 WO2018079602A1 (en) 2016-10-31 2017-10-25 Rubber composition and rubber crosslinked product

Publications (2)

Publication Number Publication Date
CN109844008A CN109844008A (en) 2019-06-04
CN109844008B true CN109844008B (en) 2021-08-24

Family

ID=62024990

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780064239.7A Active CN109844008B (en) 2016-10-31 2017-10-25 Rubber composition and crosslinked rubber

Country Status (5)

Country Link
US (1) US11267956B2 (en)
EP (1) EP3533829B1 (en)
JP (1) JP6950705B2 (en)
CN (1) CN109844008B (en)
WO (1) WO2018079602A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11390709B2 (en) * 2017-09-29 2022-07-19 Zeon Corporation Liquid copolymer formed by ring-opening copolymerization of cyclopentene, crosslinkable composition, and crosslinked rubber object
JP7294332B2 (en) * 2018-05-16 2023-06-20 日本ゼオン株式会社 Rubber composition and cross-linked rubber
JPWO2019220933A1 (en) * 2018-05-16 2021-06-24 日本ゼオン株式会社 Rubber composition and rubber crosslinked product
JP7081370B2 (en) * 2018-07-26 2022-06-07 日本ゼオン株式会社 Compositions for bending fatigue resistant materials, crosslinked products for bending fatigue resistant materials and bending fatigue resistant materials
WO2021113503A1 (en) * 2019-12-04 2021-06-10 Exxonmobil Chemical Patents Inc. Polymers prepared by ring opening metathesis polymerization
CN114787232B (en) * 2019-12-17 2024-06-07 日本瑞翁株式会社 Ring-opened copolymer
CN115551708A (en) * 2020-03-03 2022-12-30 埃克森美孚化学专利公司 Rubber compound for treads of heavy-duty trucks and buses and related method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1476424A (en) * 1973-08-14 1977-06-16 Shell Int Research Butadiene rubber compositions
EP1245630A1 (en) * 2000-08-01 2002-10-02 The Yokohama Rubber Co., Ltd. Rubber composition and crosslinked rubber
EP1552965A1 (en) * 2002-07-12 2005-07-13 Daicel-Degussa Ltd. Rubber-reinforced structure
JP2013144813A (en) * 2013-04-30 2013-07-25 Nippon Zeon Co Ltd Cyclopentene ring-opened polymer composition
WO2016060262A1 (en) * 2014-10-17 2016-04-21 日本ゼオン株式会社 Rubber composition for tire
CN106032428A (en) * 2015-03-18 2016-10-19 中国石油化工股份有限公司 Rubber composition, and vulcanized rubber and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2123452A1 (en) * 1971-05-12 1972-11-23 Farbenfabriken Bayer Ag, 5090 Leverkusen Mixtures of polyisoprene rubber and polypentenamer
DE2131354B2 (en) * 1971-06-24 1975-10-30 Chemische Werke Huels Ag, 4370 Marl Process for improving the raw strength of rubber compounds
US6060570A (en) 1996-08-12 2000-05-09 Bp Amoco Corporation Process for preparation of addition products of difunctional telechelic polyolefins from cyclic olefins by olefin metathesis reaction
JP2002317034A (en) 2001-04-20 2002-10-31 Nippon Zeon Co Ltd Hydrogenated material of norbornene ring opening polymer having functional group at terminal and method for producing the same
JP2013094914A (en) * 2011-11-02 2013-05-20 Honda Motor Co Ltd Cutting tool
JP2016079329A (en) * 2014-10-20 2016-05-16 日本ゼオン株式会社 Rubber composition for tire, rubber crosslinked article and tire
JP2016079330A (en) * 2014-10-20 2016-05-16 日本ゼオン株式会社 Rubber composition for side wall
CN106977636B (en) * 2016-01-18 2019-06-28 中国石油化工股份有限公司 A kind of trans- polycyclic amylene rubber of liquid and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1476424A (en) * 1973-08-14 1977-06-16 Shell Int Research Butadiene rubber compositions
EP1245630A1 (en) * 2000-08-01 2002-10-02 The Yokohama Rubber Co., Ltd. Rubber composition and crosslinked rubber
EP1552965A1 (en) * 2002-07-12 2005-07-13 Daicel-Degussa Ltd. Rubber-reinforced structure
JP2013144813A (en) * 2013-04-30 2013-07-25 Nippon Zeon Co Ltd Cyclopentene ring-opened polymer composition
WO2016060262A1 (en) * 2014-10-17 2016-04-21 日本ゼオン株式会社 Rubber composition for tire
CN106032428A (en) * 2015-03-18 2016-10-19 中国石油化工股份有限公司 Rubber composition, and vulcanized rubber and preparation method thereof

Also Published As

Publication number Publication date
US11267956B2 (en) 2022-03-08
EP3533829A4 (en) 2020-07-01
US20190256692A1 (en) 2019-08-22
WO2018079602A1 (en) 2018-05-03
EP3533829B1 (en) 2021-11-24
JPWO2018079602A1 (en) 2019-09-19
EP3533829A1 (en) 2019-09-04
CN109844008A (en) 2019-06-04
JP6950705B2 (en) 2021-10-13

Similar Documents

Publication Publication Date Title
CN109844008B (en) Rubber composition and crosslinked rubber
JP2019081840A (en) High-resilience material
JP2022110126A (en) Crosslinkable composition and crosslinked product
JP7206672B2 (en) Composition for fracture-resistant material, cross-linked product for fracture-resistant material, and fracture-resistant material
US10774174B2 (en) Use of crosslinked rubber
CN111133026B (en) Liquid cyclopentene ring-opening polymer, rubber composition, and rubber crosslinked product
JP6933219B2 (en) Rubber cross-linked product
JP2018028008A (en) High resilience material
JP6878786B2 (en) Rubber cross-linked product
JP7081370B2 (en) Compositions for bending fatigue resistant materials, crosslinked products for bending fatigue resistant materials and bending fatigue resistant materials
JP2018070783A (en) Gas barrier material
US11332610B2 (en) Rubber composition and crosslinked rubber
JP6862774B2 (en) Polymer composition for anti-vibration rubber, cross-linked rubber, and anti-vibration rubber
JPWO2019220932A1 (en) Rubber composition and rubber crosslinked product

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant